Curable resin composition, resin film, laminate, method for producing laminate, semiconductor package, and display device

Abstract

To provide a curable resin composition that can balance high alkali developability with high surface smoothness, a resin film formed from the curable resin composition, a laminate formed by bonding a substrate and an adherend using the curable resin composition, a method for producing the laminate, and a semiconductor package and a display device employing the resin film.SOLUTION: The present invention relates to a curable resin composition comprising (A) an unsaturated group-containing alkali-soluble resin, (E) an acrylic leveling agent, and (F) a solvent, wherein the (A) unsaturated group-containing alkali-soluble resin has an acid value of 25 mgKOH / g to 200 mgKOH / g, and the (E) acrylic leveling agent has a weight-average molecular weight of 3,000 to 40,000.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a curable resin composition, a resin film, a laminate, a method for producing a laminate, a semiconductor package, and a display device. [Background technology]

[0002] Protective films are used in semiconductor devices, image display devices, etc. to seal and protect each element on a substrate. As these protective films that require transparency and heat resistance, cured films are used that are formed by applying a curable resin composition containing an alkali-soluble resin having an unsaturated group, patterning, and curing the composition (for example, Patent Document 1, etc.). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2012-106486 A Summary of the Invention [Problem to be solved by the invention]

[0004] When forming a coating film of a photosensitive resin composition on a substrate, a coating device such as a spin coater, a slit & spin coater, a slit coater, a roll coater, or a bar coater is used. In recent years, high in-plane film thickness uniformity of a cured film has been required, and a technology for imparting high surface smoothness to a coating film is required. However, according to the study by the present inventors, when a coating film is formed using the resin composition described in Patent Document 1, a coating film satisfying the desired surface smoothness could not be obtained.

[0005] In order to improve the surface smoothness of a coating film, a method of adding a leveling agent to a composition is common. However, in the field of semiconductors, for example, when a silicone-based leveling agent is used, the outgas generated by the silicone-based leveling agent may cause defects such as contact failure. In this way, in the field of semiconductors, the materials that can be used as a leveling agent are limited, and acrylic leveling agents that are less likely to cause failures are being considered. However, in the combination of an acrylic leveling agent and an alkali-developable resin, there is a problem that it is difficult to achieve both the alkali developability of the resin film and surface smoothness.

[0006] The present invention has been made in consideration of the above points, and has an object to provide a curable resin composition that can achieve both high alkaline developability and high surface smoothness, a resin film formed from the curable resin composition, a laminate obtained by bonding a support and an adherend using the curable resin composition, a method for producing the laminate, and a semiconductor package and a display device that use the resin film. [Means for solving the problem]

[0007] In order to solve the above problems, the present inventors conducted extensive research and found that a curable resin composition containing an unsaturated group-containing alkali-soluble resin whose acid value is adjusted to a predetermined range and further using an acrylic leveling agent with a relatively high weight average molecular weight is suitable as a resin film, thereby completing the present invention.

[0008] The reason for this is not entirely clear, but is believed to be as follows. By increasing the amount of alkali-soluble groups introduced into the resin, the alkali solubility of the resin can be increased. Furthermore, by appropriately increasing the weight-average molecular weight of the acrylic leveling agent, the mixing free energy between the acrylic-soluble resin and the acrylic leveling agent can be controlled, and the surface segregation property of the acrylic leveling agent can be increased. In this way, it is believed that a curable resin composition that combines high alkali developability and high surface smoothness can be provided.

[0009] That is, the above problem can be solved by the following configuration.

[0010] [1] (A) an unsaturated group-containing alkali-soluble resin; (E) an acrylic leveling agent; (F) a solvent; Including, The (A) unsaturated group-containing alkali-soluble resin has an acid value of 25 mgKOH / g to 200 mgKOH / g, The (E) acrylic leveling agent has a weight average molecular weight of 3,000 to 40,000. Curable resin composition.

[0011] [2] the ratio [Mw(E)] / [Mw(A)] of the weight average molecular weight [Mw(E)] of the (E) acrylic leveling agent to the weight average molecular weight [Mw(A)] of the (A) unsaturated group-containing alkali-soluble resin is 0.5 to 12.0; The curable resin composition according to [1].

[0012] [3] The polar term δ of the Hansen solubility parameter of the (E) acrylic leveling agent P But 4.0MPa 1 / 2 ~10.0MPa 1 / 2 That is, The curable resin composition according to [1] or [2].

[0013] [4] The content of the (E) acrylic leveling agent is 0.10% by mass to 0.90% by mass based on the total mass of the solid content of the curable resin composition. The curable resin composition according to any one of [1] to [3].

[0014] [5] (B) a polymerizable compound having at least two unsaturated groups; (C) an epoxy compound having at least two substituents selected from the group consisting of an oxirane group and an oxetane group; The curable resin composition according to any one of [1] to [4],

[0015] [6] A resin film formed from the curable resin composition according to any one of [1] to [5].

[0016] [7] A support; An adherend; an adhesive layer including a resin film of the curable resin composition according to any one of [1] to [5], which is disposed between the support and the adherend; A laminate having the following structure:

[0017] [8] A step of forming an adhesive layer on one or both of a surface of a support and an adherend using the curable resin composition according to any one of [1] to [5]; a step of adhering the support and the adherend via the formed adhesive layer; A method for producing a laminate comprising the steps of:

[0018] [9] A semiconductor package comprising the resin film according to [6] as an insulating film.

[0019]

[10] A display device comprising the resin film according to [6] as an insulating film. Effect of the Invention

[0020] According to the present invention, there are provided a curable resin composition that can achieve both high alkaline developability and high surface smoothness, a resin film formed from the curable resin composition, a laminate obtained by adhering a support and an adherend using the curable resin composition, a method for producing the laminate, and a semiconductor package and a display device that use the resin film. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] Hereinafter, an embodiment of the present invention will be described, but the present invention is not limited to the following embodiment. In addition, in the present invention, when the first decimal place of the content of each component is 0, the notation after the decimal point may be omitted.

[0022] In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits.

[0023] 1. Curable resin composition The curable resin composition according to the present embodiment is (A) an unsaturated group-containing alkali-soluble resin (hereinafter also referred to simply as “component (A)”), (E) an acrylic leveling agent (hereinafter also referred to simply as “component (E)”), (F) a solvent (hereinafter also referred to simply as "component (F)"); Each component will be described below.

[0024] 1-1.(A) Alkali-soluble resin containing unsaturated groups The component (A) has a polymerizable unsaturated group and an acidic group for exhibiting alkali solubility, and has an acid value of 25 mgKOH / g to 200 mgKOH / g. Such a resin is not particularly limited and can be widely used. By using such a resin, the alkali developability can be improved.

[0025] The polymerizable unsaturated group of component (A) is not particularly limited as long as it is a functional group having an unsaturated bond, but is preferably a (meth)acryloyl group, which can enhance curability and impart good alkali resistance.

[0026] In addition, the term "(meth)acryloyl group" is a general term for an acryloyl group and a methacryloyl group, "(meth)acrylic acid" is a general term for an acrylic acid and a methacrylic acid, and "(meth)acrylate" is a general term for an acrylate and a methacrylate, and each refers to one or both of these.

[0027] Examples of the acidic group that is possessed by the component (A) for expressing the alkali solubility include a carboxy group, a phosphate group, and a sulfonic acid group, and the like. From the viewpoints of increasing the solubility in an alkaline developer and suppressing the formation of residues in unexposed areas, a carboxy group is preferred.

[0028] The curable resin composition according to the present embodiment can also be used as an adhesive for use in a laser lift-off process (hereinafter, also simply referred to as an "LLO process"). When used in an LLO process, it is preferable that the component (A) absorbs light well. When the component (A) absorbs the laser well and generates heat, the component (A) changes or decomposes, and the adherend can be peeled off well. The light to be absorbed is preferably ultraviolet light, more preferably light with a wavelength of 10 nm to 400 nm, even more preferably light with a wavelength of 100 nm to 400 nm, and most preferably light with a wavelength of 200 nm to 400 nm.

[0029] The acid value of component (A) is 25 mgKOH / g to 200 mgKOH / g, and preferably 50 mgKOH / g to 150 mgKOH / g. When the acid value is 25 mgKOH / g or more, it is possible to easily improve the alkaline developability. By making the acid value smaller, it is possible to appropriately lower the polarity of component (A), and to easily improve the compatibility with component (E). The acid value can be determined by titration with a 1 / 10N-KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

[0030] The weight average molecular weight (Mw) of the component (A) in terms of polystyrene as measured by gel permeation chromatography (GPC) (HLC-8220GPC, manufactured by Tosoh Corporation) is usually preferably 1000 to 100000, more preferably 1500 to 50000, and even more preferably 2000 to 40000. When the weight average molecular weight (Mw) is 1000 or more, the adhesion to the substrate can be improved and peeling of the pattern during development can be easily suppressed. When the weight average molecular weight (Mw) is less than 100000, the compatibility with the component (E) can be easily improved.

[0031] In the curable resin composition of the present embodiment, the content of the component (A) is preferably 10% by mass to 80% by mass, more preferably 30% by mass to 80% by mass, and even more preferably 50% by mass to 80% by mass, based on the total mass of the solid content. When the content of the component (A) is 10% by mass or more based on the total mass of the solid content, it is possible to easily improve the alkaline developability. Furthermore, when it is 80% by mass or less, the compatibility with the component (E) is improved, and it is possible to easily reduce the haze.

[0032] Exemplary compounds of the component (A) that are preferably used in the curable resin composition of this embodiment are listed below, but are not limited to the following compounds.

[0033] 1-1-1. Example compound 1 of component (A) The component (A) is preferably an alkali-soluble resin containing a polymerizable unsaturated group obtained by further reacting a reaction product of an epoxy compound having two or more epoxy groups with (meth)acrylic acid with a polybasic carboxylic acid or an anhydride thereof. During the production of the alkali-soluble resin, a polyester is generated by the reaction of a hydroxyl group with a polybasic carboxylic acid, and the average degree of polymerization is preferably a low molecular weight of about 2 to 500.

[0034] The epoxy compound is preferably an epoxy compound having two or more epoxy groups. Examples of such epoxy compounds include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol fluorene type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds (e.g., EPPN-501H: manufactured by Nippon Kayaku Co., Ltd.), phenol aralkyl type epoxy compounds, phenol novolac compounds containing a naphthalene skeleton (e.g., NC-7000L: manufactured by Nippon Kayaku Co., Ltd.), biphenyl type epoxy compounds (e.g., jER YX4000: manufactured by Mitsubishi Chemical Corporation), naphthol aralkyl type epoxy compounds, trisphenol methane type epoxy compounds, tetrakisphenol ethane type epoxy compounds, glycidyl ethers of polyhydric alcohols, glycidyl esters of polycarboxylic acids, copolymers of monomers having (meth)acrylic groups containing glycidyl (meth)acrylate as a unit, such as copolymers of methacrylic acid and glycidyl methacrylate, 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate (e.g., Celloxide 2021P: manufactured by Daicel Corporation), butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl) modified ε-caprolactone (for example, Epolead GT401: manufactured by Daicel Corporation), epoxy compounds having an epoxycyclohexyl group such as HiREM-1 manufactured by Shikoku Chemical Industry Co., Ltd., polyfunctional epoxy compounds having a dicyclopentadiene skeleton (for example, HP7200 series: manufactured by DIC Corporation), 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (for example, EHPE3150: manufactured by Daicel Corporation), epoxidized polybutadiene (for example, NISSO-PB·JP-100: manufactured by Nippon Soda Co., Ltd.), and epoxy compounds having a silicone skeleton.

[0035] From the viewpoint of appropriately suppressing the penetration of the developer, increasing the adhesion to the substrate, and suppressing the peeling of the pattern during development, it is preferable that the (A) component has at least one aromatic ring and alicyclic structure in the molecule. From the above viewpoint, it is more preferable that the (A) component has a plurality of aromatic rings, and it is further preferable that the (A) component is an alkali-soluble resin having a repeating unit containing a fluorene structure, and it is most preferable that the (A) component is an alkali-soluble resin having a repeating unit containing a bisarylfluorene skeleton. From the same viewpoint, for example, the (A) component is preferably a resin represented by the following general formula (1).

[0036] [ka]

[0037] In formula (1), each Ar is independently an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a portion of the bonded hydrogen atoms may be substituted with a substituent selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group or arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl group or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen group. 1 are each independently an alkylene group having 2 to 4 carbon atoms, and each 1 is independently a number from 0 to 3. G is each independently a (meth)acryloyl group or a substituent represented by the following general formula (2) or the following general formula (3), and Y is a tetravalent carboxylic acid residue. Z is each independently a hydrogen atom or a substituent represented by the following general formula (4), and at least one Z is a substituent represented by the following general formula (4). n is a number with an average value of 1 to 20.

[0038] [ka]

[0039] [ka]

[0040] In formulas (2) and (3), R 2 is a hydrogen atom or a methyl group, R 3 is a divalent alkylene or alkylarylene group having 2 to 10 carbon atoms, R 4 is a divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and p is a number from 0 to 10. * indicates a bonding site.

[0041] [ka]

[0042] In formula (4), W is a divalent or trivalent carboxylic acid residue, and m is the number 1 or 2. * indicates a bonding site.

[0043] In addition, when used in the LLO process, Y represented by the above general formula (1) preferably contains at least one aromatic hydrocarbon group. Examples of the aromatic hydrocarbon group include a phenyl group, a biphenyl group, a benzophenone group, a naphthalene group, and a biphenyl ether group. Among the above aromatic hydrocarbon groups, a biphenyl group, a benzophenone group, or a naphthalene group is preferable. When Y is an aromatic hydrocarbon group, the absorbance of the resin at a wavelength of 260 nm to 400 nm can be improved, and the alteration or decomposition of the cured film caused by the irradiation of a laser can be more effectively promoted.

[0044] The acid value of the component (A) represented by the general formula (1) is 25 mgKOH / g to 200 mgKOH / g, and preferably 50 mgKOH / g to 150 mgKOH / g. When the acid value is 25 mgKOH / g or more, it is possible to easily improve the alkaline developability. By reducing the acid value, it is possible to appropriately reduce the polarity of the component (A), and to easily improve the compatibility with the component (E). The acid value can be determined by titration with a 1 / 10N-KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

[0045] The weight average molecular weight (Mw) of the component (A) represented by the above general formula (1) in terms of polystyrene, as measured by gel permeation chromatography (GPC) (HLC-8220GPC, manufactured by Tosoh Corporation), is usually preferably 1000 to 100000, more preferably 1500 to 30000, and even more preferably 2000 to 10000. When the weight average molecular weight (Mw) is 1000 or more, the adhesion to the substrate can be improved and peeling of the pattern during development can be suppressed. When the weight average molecular weight (Mw) is less than 100000, the compatibility with the component (E) can be improved while the surface segregation of the component (E) can be easily improved.

[0046] The component (A) represented by the above general formula (1) can be produced by a known method. For example, referring to the production method described in paragraphs

[0026] to

[0063] of JP 2022-065426 A, a diol (d) containing a polymerizable unsaturated group obtained by reacting an epoxy compound having a bisarylfluorene skeleton with a (meth)acrylic acid derivative, a dicarboxylic acid or tricarboxylic acid or its monoanhydride (b), and a tetracarboxylic acid or its dianhydride (c) can be reacted to obtain an alkali-soluble resin having a carboxy group and a polymerizable unsaturated group in one molecule.

[0047] Here, it is preferable to react the diol (d) having a polymerizable unsaturated group, the dicarboxylic acid or tricarboxylic acid or an acid monoanhydride thereof (b), and the tetracarboxylic acid dianhydride (c) so that the molar ratio of (d):(b):(c) is 1.0:0.01-1.0:0.2-1.0.

[0048] For example, when using an acid monoanhydride (b) and an acid dianhydride (c), it is preferable to react them so that the molar ratio [[(b) / 2+(c)] / (d)] of the diol (d) containing a polymerizable unsaturated group to the amount of the acid component [(b) / 2+(c)] is 0.5 to 1.0. Here, when the molar ratio exceeds 0.5, the content of the diol containing an unreacted polymerizable unsaturated group is not increased, so the stability over time of the alkali-soluble resin composition can be improved. On the other hand, when the molar ratio is 1.0 or less, the terminal of the alkali-soluble resin represented by the general formula (1) does not become an acid anhydride, so that the content of the unreacted acid dianhydride can be suppressed from increasing, so the stability over time of the alkali-soluble resin composition can be improved. In addition, in order to adjust the acid value and molecular weight of the alkali-soluble resin represented by the general formula (1), the molar ratios of each component (b), (c) and (d) can be arbitrarily changed within the above-mentioned range.

[0049] 1-1-2. Example compound 2 of component (A) As the component (A), a (meth)acrylic copolymer is also preferably used.

[0050] The component (A) may be, for example, a (meth)acrylic copolymer formed by combining any or all of the following structural units (AA) to (AE) derived from different monomers. The (meth)acrylic copolymer includes the structural units (AB) and (AC) among these. (AA) Structural unit having an ultraviolet absorbing group (AB) a structural unit having a polymerizable unsaturated group and no carboxy group (AC) a structural unit having a carboxy group and no polymerizable unsaturated group (AE) a structural unit having no ultraviolet absorbing group, no polymerizable unsaturated group, and no carboxy group

[0051] The structural unit (AA) is a structural unit having an ultraviolet absorbing group, and the (meth)acrylic copolymer preferably contains the structural unit (AA). By containing the structural unit (AA), light can be absorbed well and laser peelability can be improved. The structural unit (AA) may have the ultraviolet absorbing group in the main chain or in the side chain of the (meth)acrylic copolymer, but from the viewpoint of ease of production of the (meth)acrylic copolymer, it is preferable that the structural unit (AA) has the ultraviolet absorbing group in the side chain.

[0052] The ultraviolet absorbing group includes functional groups having a benzotriazole structure, a benzophenone structure in which a portion of the hydrogen atoms contained in the benzene ring is substituted with a hydroxyl group (hereinafter, also simply referred to as a "substituted benzophenone structure"). A triazine structure, a salicylic acid structure, a benzoate structure, a cinnamic acid derivative structure, a diphenyl sulfoxide structure, a diphenyl sulfone structure, a diphenyl structure, a diphenylamine structure, a naphthalene derivative structure, a structure based on anthracene and its derivatives, a structure having a dinaphthalene structure, and a structure having a phenanthroline structure. Among these, functional groups having a benzotriazole structure, a substituted benzophenone structure, or a triazine structure are preferred, as they efficiently absorb 355 nm ultraviolet light, functional groups having a benzotriazole structure or a triazine structure are more preferred, and functional groups having a benzotriazole structure (hydroxyphenylbenzotriazole structure) are more preferred.

[0053] The structural unit (AA) preferably does not have a polymerizable unsaturated group, and preferably does not have a carboxy group.

[0054] The structural unit (AB) is a structural unit having a polymerizable unsaturated group.

[0055] Examples of the polymerizable unsaturated group include a vinyl group, an allyl group, and a (meth)acryloyl group, etc. Among these, a (meth)acryloyl group is preferred.

[0056] The polymerizable unsaturated group is preferably grafted to the side chain of the structural unit (AB). In other words, the polymerizable unsaturated group is preferably bonded to the side chain of the structural unit (AB) via a linking group or linking structure generated during grafting. Examples of the linking group or linking structure include an ester bond, a urethane bond, and an epoxy acrylate residue. Among these, the polymerizable unsaturated group is preferably grafted to the side chain via a urethane bond or an epoxy acrylate residue, because grafting is easy. From the viewpoint of further increasing the compatibility of the (meth)acrylic copolymer with other alkali-soluble resins (e.g., alkali-soluble resins having a fluorene skeleton), the polymerizable unsaturated group is preferably grafted to the side chain via a urethane bond, and from the viewpoint of making it easier to adjust the development speed, the polymerizable unsaturated group is preferably grafted to the side chain via an epoxy acrylate residue.

[0057] It is preferable that the structural unit (AB) does not have an ultraviolet absorbing group.

[0058] The structural unit (AC) is a structural unit having a carboxy group.

[0059] The carboxy group may be a functional group derived from a monomer (e.g., (meth)acrylic acid, etc.) that is a material of the structural unit (AC), or may be grafted to a side chain in the structural unit (AC). In other words, the carboxy group may be bonded to a side chain in the structural unit (AC) via a linking group or linking structure generated during grafting. From the viewpoint of making it easier to adjust the development rate, it is preferable that the carboxy group is grafted to a side chain in the structural unit (AC). Examples of the linking group or linking structure include an ester bond, a urethane bond, and an epoxy acrylate residue. Among these, from the viewpoint of facilitating grafting, it is preferable that the carboxy group is grafted to a side chain via a urethane bond or an epoxy acrylate residue, and from the viewpoint of increasing the development rate, it is preferable that the carboxy group is grafted to a side chain via an ester bond.

[0060] It is preferable that the structural unit (AC) does not have an ultraviolet absorbing group.

[0061] The structural unit (AE) is a structural unit that is optionally introduced for the purposes of adjusting the molecular weight and adjusting the amounts of each functional group, ie, the ultraviolet absorbing group, the polymerizable unsaturated group, and the carboxy group.

[0062] The structural unit (AE) may be a structural unit derived from a monomer that does not have any of the above functional groups. In order to adjust the physical properties of the (meth)acrylic copolymer, the structural unit may be a structural unit to which a functional group different from the above functional groups has been grafted.

[0063] Each of the above structural units may be modified with an alkylene oxide or a lactone.

[0064] Specific examples of the (meth)acrylic copolymer include a copolymer in which the structural unit (AA) is a structural unit represented by the following general formula (A-1), the structural unit (AB) is a structural unit represented by the following general formula (A-2), the structural unit (AC) is a structural unit represented by the following general formula (A-3), and the structural unit (AE) is a structural unit represented by the following general formula (A-4).

[0065] [ka]

[0066] [ka]

[0067] [ka]

[0068] [ka]

[0069] In general formulas (A-1) to (A-4), R 11 ~R 14 and R 19 represents a hydrogen atom or a methyl group, of which a methyl group is preferred.

[0070] R 15 ~R 18 and R 20 ~R 21 represents a hydrocarbon group having 1 to 10 carbon atoms which may have a cyclic structure or an aromatic ring, may have a substituent, may have an ether bond, and may have an unsaturated bond.

[0071] R 22 R represents a hydrocarbon group having 1 to 30 carbon atoms, which may have a cyclic structure or an aromatic ring, may have a substituent, may be modified with an alkylene oxide, and may have one or two heteroatoms. 22 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms which may have a substituent.

[0072] X 1 represents an epoxy acrylate residue having a secondary hydroxyl group, an ester bond, or a urethane bond. Among these, an ester bond and a urethane bond are preferred, and an ester bond is more preferred.

[0073] X 2 and X 3 each independently represents an epoxy acrylate residue having a secondary hydroxyl group, an ester bond, or a urethane bond. Among these, a urethane bond is preferred.

[0074] X 1 ~X 3 are preferably bonds or structures different from each other.

[0075] U represents an ultraviolet absorbing group. The ultraviolet absorbing group may be any functional group having the structure exemplified as the ultraviolet absorbing group contained in the structural unit (AA).

[0076] * indicates the bonding site with other structural units.

[0077] The (meth)acrylic copolymer can be synthesized by copolymerizing an appropriate combination of the following monomers, and then grafting an ultraviolet absorbing group, a polymerizable unsaturated group, or a carboxy group onto the side chains of the structural units derived from the monomers (Ax1) to (Ax3). (Aa) A monomer having a (meth)acryloyl group and an ultraviolet absorbing group (Ac) A monomer having a (meth)acryloyl group and a carboxy group (Ae) A monomer having a (meth)acryloyl group and having neither an ultraviolet absorbing group nor a carboxy group. (Ax1) A monomer having a (meth)acryloyl group and a hydroxyl group (Ax2) A monomer having a (meth)acryloyl group and an isocyanate group (Ax3) A monomer having a (meth)acryloyl group and a glycidyl group or an alicyclic epoxy group

[0078] The monomer (Aa) is a monomer for introducing an ultraviolet absorbing group into the (meth)acrylic copolymer.

[0079] From the viewpoint of increasing the ultraviolet absorbing ability of the (meth)acrylic copolymer, the monomer (Aa) is preferably a monomer having a molar absorption coefficient of 3000 L / (mol·cm) or more at a wavelength of 355 nm. From the same viewpoint, the monomer (Aa) is more preferably a monomer having a molar absorption coefficient of 3000 L / (mol·cm) to 100000 L / (mol·cm) at a wavelength of 355 nm, further preferably a monomer having a molar absorption coefficient of 4000 L / (mol·cm) to 90000 L / (mol·cm), and particularly preferably a monomer having a molar absorption coefficient of 5000 L / (mol·cm) to 80000 L / (mol·cm). The molar absorption coefficient can be measured under the same conditions as those for measuring the molar absorption coefficient described above.

[0080] Examples of monomer (Aa) include compounds described in JP-A-2004-182924, JP-A-2007-286123, JP-A-2007-331359, JP-A-2013-204001, JP-A-2015-124254, JP-A-2019-137844, and JP-A-2020-189906.

[0081] The monomer (Ac) is a monomer for introducing a carboxy group into the (meth)acrylic copolymer. The monomer (Ac) is preferably a monomer that does not have the above-mentioned ultraviolet absorbing group. The monomer (Ac) is preferably a monomer that has a molar absorption coefficient at a wavelength of 355 nm of less than 3000 L / (mol cm). The molar absorption coefficient can be measured under the same conditions as those for measuring the molar absorption coefficient described above.

[0082] Examples of monomers (Ac) include (meth)acrylic acid, succinic acid mono(2-(meth)acryloyloxyethyl), hexahydrophthalic acid(2-(meth)acryloyloxyethyl), phthalic acid(2-(meth)acryloyloxyethyl), maleic acid(2-(meth)acryloyloxyethyl), fumaric acid(2-acryloyloxyethyl), itaconic acid(2-(meth)acryloyloxyethyl). , citraconic acid (2-(meth)acryloyloxyethyl), carboxyethyl (meth)acrylate, 3-carboxypropyl (meth)acrylate, 4-carboxybutyl (meth)acrylate, mono n-butyl maleate (2-(meth)acryloyloxyethyl), mono n-butyl fumarate (2-(meth)acryloyloxyethyl), and mono n-butyl itaconate (2-(meth)acryloyloxyethyl).

[0083] The monomer (Ae) is a monomer for adjusting the molecular weight and the amount of functional groups of the (meth)acrylic copolymer.

[0084] Examples of the monomer (Ae) include those having an alkyl chain having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as ethyl (meth)acrylate, methyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, isopentyl (meth)acrylate, neopentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate. (Meth)acrylate, methoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, 2-ethylhexyl diglycol (meth)acrylate, butoxydiethylene glycol (meth)acrylate and other alkylene oxide-modified (meth)acrylates having an alkyl chain having 1 to 10 carbon atoms, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, cyclododecyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantan-1-yl (meth)acrylate, 4-t-butylcyclohexyl (meth)acrylate, 3,3,(Meth)acrylates having alicyclic hydrocarbons with 3 to 30 carbon atoms, such as 5-trimethylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenylethyl (meth)acrylate, phenoxyethyl (meth)acrylate, 2-biphenyl (meth)acrylate, (meth)acrylates having aromatic hydrocarbons with 3 to 30 carbon atoms, such as 2-naphthyl (meth)acrylate, neopentyl glycol-acrylic acid-benzoic acid ester, phenoxyethylene glycol methacrylate, ethoxylated-O-phenyl Examples of the (meth)acrylate include alkylene oxide-modified aromatic hydrocarbon having 3 to 30 carbon atoms, such as phenol (meth)acrylate, phthalimide (meth)acrylate, maleimide (meth)acrylate, benzophenone (meth)acrylate, 2-hydroxy-4-(meth)acryloyloxybenzophenone, and hydroxy-4-(2-(meth)acryloyloxy)ethoxybenzophenone, and other (meth)acrylates having a hydrocarbon group having 1 to 30 carbon atoms which may have one or two heteroatoms.

[0085] The monomers (Ax1) to (Ax3) are monomers for introducing the above-mentioned functional group into the side chain of the (meth)acrylic copolymer by grafting.

[0086] The monomers (Ax1) to (Ax3) are preferably monomers that do not have the above-mentioned ultraviolet absorbing group. Moreover, the monomers (Ax1) to (Ax3), and the monomer (Aa) are preferably monomers that have a molar absorption coefficient at a wavelength of 355 nm of less than 3000 L / (mol cm). Moreover, the monomers (Ax1) to (Ax3) are preferably monomers that do not have a carboxy group. The molar absorption coefficient can be measured under the same conditions as those for measuring the molar absorption coefficient described above.

[0087] For example, a monomer (Ax1) having a hydroxyl group can be used, after copolymerization with other monomers, to introduce a polymerizable unsaturated group into a (meth)acrylic copolymer via a urethane bond by reacting a compound (Ay1a) having an isocyanate group and a polymerizable unsaturated group with the hydroxyl group.

[0088] Alternatively, the monomer (Ax1) having a hydroxyl group can be used for introducing a carboxyl group into the (meth)acrylic copolymer via an ester bond by reacting the hydroxyl group with (Ay1b) a dicarboxylic acid or an acid monoanhydride thereof after copolymerization with another monomer.

[0089] Examples of such monomers (Ax1) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, and ethyl-α-hydroxymethyl acrylate.

[0090] Examples of the compound having an isocyanate group and a polymerizable unsaturated group (Ay1a), which is used together with the monomer (Ax1), include (2-(meth)acryloyloxyethyl)isocyanate.

[0091] Examples of the dicarboxylic acid (Ay1b) or the acid monoanhydride thereof used together with the monomer (Ax1) include open-chain hydrocarbon dicarboxylic acids, alicyclic hydrocarbon dicarboxylic acids, aromatic hydrocarbon dicarboxylic acids, and the acid monoanhydrides thereof.

[0092] It is preferable to use the dicarboxylic acid as its monoanhydride.

[0093] In addition, the monomer (Ax2) having an isocyanate group can be used for introducing a polymerizable unsaturated group into the (meth)acrylic copolymer via a urethane bond by reacting (Ay2) a compound having a hydroxyl group and a polymerizable unsaturated group with the isocyanate group after copolymerization with other monomers.

[0094] Examples of such a monomer (Ax2) include the compounds exemplified above as the compound having an isocyanate group and a polymerizable unsaturated group.

[0095] Examples of the compound (y2) having a hydroxyl group and a polymerizable unsaturated group, which is used together with the monomer (Ax2), include the compounds exemplified as the monomer (Ax1).

[0096] Instead of the compound having a hydroxyl group and a polymerizable unsaturated group (Ay2), a compound having a hydroxyl group and an ultraviolet absorbing group or a compound having a hydroxyl group and a carboxy group may be used to introduce the ultraviolet absorbing group or the carboxy group into the side chain of the structural unit derived from the monomer (Ax2) via a urethane bond.

[0097] Furthermore, the monomer (Ax3) having a glycidyl group or an alicyclic epoxy group can be used for introducing a polymerizable unsaturated group into the (meth)acrylic copolymer via an epoxy acrylate residue by reacting (Ay3) a compound having a carboxy group and a polymerizable unsaturated group with the glycidyl group or the alicyclic epoxy group after copolymerization with other monomers.

[0098] Examples of such monomers (Ax3) include glycidyl (meth)acrylate, β-propyl glycidyl (meth)acrylate, β-methyl glycidyl-α-ethyl (meth)acrylate, 3-methyl-3,4-epoxybutyl (meth)acrylate, 4-methyl-4,5-epoxypentyl (meth)acrylate, 5-methyl-5,6-epoxyhexyl (meth)acrylate, and 3,4-epoxycyclohexylmethyl methacrylate.

[0099] Examples of the compound (Ay3) having a carboxy group and a polymerizable unsaturated group, which is used together with the monomer (Ax3), include the compounds exemplified as the monomer (Ac).

[0100] The acid value of the (meth)acrylic copolymer is 25 mgKOH / g to 200 mgKOH / g, preferably 50 mgKOH / g to 150 mgKOH / g. When the acid value is 25 mgKOH / g or more, it is possible to easily improve the alkaline developability. When the acid value is small, it is possible to appropriately lower the polarity of the (A) component, and to easily improve the compatibility with the (E) component. The acid value can be determined by titration with a 1 / 10N-KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

[0101] The weight average molecular weight (Mw) of the (meth)acrylic copolymer, measured by gel permeation chromatography (GPC) (HLC-8220GPC, manufactured by Tosoh Corporation) in terms of polystyrene, is preferably 1000 to 100000, more preferably 1500 to 50000, and even more preferably 2000 to 40000. When the weight average molecular weight (Mw) is 1000 or more, the adhesion to the substrate can be improved and the peeling of the pattern during development can be suppressed. When the weight average molecular weight (Mw) is less than 100000, the surface segregation of the (E) component can be easily increased within a range that does not deteriorate the compatibility with the (E) component.

[0102] In the curable resin composition of the present embodiment, the content of the (meth)acrylic copolymer is preferably 10% by mass to 80% by mass, more preferably 30% by mass to 80% by mass, and even more preferably 50% by mass to 80% by mass, based on the total mass of the solid content. When the content of the (A) component is 10% by mass or more based on the total mass of the solid content, it is possible to easily improve the alkaline developability. Furthermore, when it is 80% by mass or less, the compatibility with the (E) component is improved, and it is possible to easily reduce the haze.

[0103] The (meth)acrylic copolymer can be produced by a known method. For example, the production methods described in paragraphs

[0013] to

[0014] of JP 2014-111722 A and paragraphs

[0032] to

[0047] of JP 2018-141968 A can be used as reference.

[0104] 1-2.(B) Polymerizable compound having at least two unsaturated groups The polymerizable compound (B) having at least two unsaturated groups (hereinafter also referred to as "component (B)") enhances the photocurability of the curable resin composition and also facilitates increasing the adhesive strength and solvent resistance of the resin film formed from the curable resin composition. Component (B) may have an unsaturated group that can react (polymerize) with an unsaturated group in component (A) or an unsaturated group in another molecule of the curable resin composition of component (B).

[0105] From the viewpoint of enhancing adhesive strength, the component (B) is preferably liquid at 25° C. When the component (B) is liquid at 25° C., the liquidity of the coating film of the curable resin composition is easily enhanced. As a result, when used in the LLO process, the coating film of the curable resin composition conforms to the irregularities of the adherend surface, and the adhesive strength of the resin film formed from the curable resin composition can be improved.

[0106] The content of the (B) component is preferably 10% by mass to 230% by mass, and more preferably 25% by mass to 120% by mass, based on the mass of the (A) component. When the content of the (B) component is 10% by mass or more based on the mass of the (A) component, the photocurability of the coating film of the curable resin composition is improved, and a sharp pattern with high resolution can be easily formed. When the content is 230% by mass or less, the solubility in the developer is not too high, making it easier to suppress pattern peeling during development.

[0107] The polymerizable unsaturated group is preferably the same functional group as the polymerizable unsaturated group of the (A) component. Specifically, the polymerizable unsaturated group is preferably a (meth)acryloyl group. The (B) component may be a monomer, an oligomer, or a polymer. The (B) component is preferably a monomer or an oligomer.

[0108] Examples of the (B) component include (meth)acrylic acid esters such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, glycerol di(meth)acrylate, glycerol tri(meth)acrylate, sorbitol penta(meth)acrylate, sorbitol hexa(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. Examples of the epoxy (meth)acrylate include urethane acrylate monomers such as rithritol triacrylate toluene diisocyanate urethane prepolymer, pentaerythritol triacrylate hexamethylene isocyanate urethane prepolymer, pentaerythritol triacrylate isophorone diisocyanate urethane prepolymer, and dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer; epoxy (meth)acrylates such as bisphenol A type epoxy (meth)acrylate, bisphenol F type epoxy (meth)acrylate, bisphenol fluorene type epoxy (meth)acrylate, diphenyl fluorene type epoxy (meth)acrylate, phenol novolac type epoxy (meth)acrylate, cresol novolac type epoxy (meth)acrylate, and phenol aralkyl type epoxy (meth)acrylate; and dendritic polymers having a (meth)acrylic group.

[0109] The (B) component preferably has two or more (meth)acryloyl groups, and more preferably has three or more (meth)acryloyl groups. When the (B) component has two or more (meth)acryloyl groups, the crosslink density is improved, and the solvent resistance of the resin film is easily improved.

[0110] The acrylic equivalent of the (B) component is preferably 50 g / eq to 500 g / eq, more preferably 70 g / eq to 450 g / eq, and even more preferably 70 g / eq to 400 g / eq. When the acrylic equivalent of the photopolymerizable compound is 500 g / eq or less, the sensitivity to radiation (e.g., ultraviolet light) is increased, and the pattern adhesion during development is easily improved. In addition, the crosslink density is increased, so that the chemical resistance can be easily improved. When the acrylic equivalent is 50 g / eq or more, it is easy to suppress the jaggedness of the pattern edge due to excessive photocuring. The acrylic equivalent of the photopolymerizable compound can be determined, for example, by dividing the molecular weight by the number of acrylic functional groups. In addition, the weight average molecular weight (Mw) of the photopolymerizable compound can be determined, for example, by using the above-mentioned gel permeation chromatography (GPC) "HLC-8220GPC".

[0111] 1-3. (C) Epoxy compounds having at least two substituents selected from the group consisting of oxirane groups and oxetane groups (C) An epoxy compound having at least two substituents selected from the group consisting of an oxirane group and an oxetane group (hereinafter also referred to as "component (C)") improves the toughness of the cured film by reacting with the alkali-soluble group of component (A) and the like, and also facilitates increasing solvent resistance such as alkali resistance. Component (C) is not particularly limited as long as it is an epoxy compound having at least two substituents selected from an oxirane group, which is a three-membered cyclic ether, and an oxetane group, which is a four-membered cyclic ether.

[0112] The component (C) can be used according to the purpose, and when used for an insulating film, it preferably contains an alicyclic structure from the viewpoint of improving light transmittance, and when used for an LLO process, it preferably has an aromatic ring structure from the viewpoint of improving laser peelability.

[0113] Of the (C) components containing oxirane groups, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol fluorene type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, biphenyl type epoxy compounds, and fluorene type epoxy compounds are preferred.

[0114] Examples of the component (C) containing an oxirane group include bisphenol A type epoxy compounds (e.g., jER 828: manufactured by Mitsubishi Chemical Corporation), bisphenol F type epoxy compounds, bisphenol fluorene type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds (e.g., EPPN-501H: manufactured by Nippon Kayaku Co., Ltd.), phenol aralkyl type epoxy compounds, phenol novolac compounds containing a naphthalene skeleton (e.g., NC-7000L: manufactured by Nippon Kayaku Co., Ltd.), biphenyl type epoxy compounds (e.g., jER YX4000: manufactured by Mitsubishi Chemical Corporation), naphthol aralkyl type epoxy compounds, trisphenolmethane type epoxy compounds, tetrakisphenolethane type epoxy compounds, glycidyl ethers of polyhydric alcohols (e.g., Epolite 100MF: manufactured by Kyoeisha Chemical Co., Ltd.), glycidyl esters of polycarboxylic acids, copolymers of monomers having (meth)acrylic groups containing glycidyl (meth)acrylate as a unit, such as copolymers of methacrylic acid and glycidyl methacrylate, 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate (e.g., Celloxide 2021P: manufactured by Daicel Corporation), butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl) modified ε-caprolactone (e.g., Epolead GT401: manufactured by Daicel Corporation), epoxy compounds having epoxycyclohexyl groups such as HiREM-1 manufactured by Shikoku Kasei Kogyo Co., Ltd., polyfunctional epoxy compounds having a dicyclopentadiene skeleton (e.g., HP7200 series: manufactured by DIC Corporation), 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (e.g., EHPE3150: manufactured by Daicel Corporation), epoxidized polybutadiene (e.g., NISSO-PB·JP-100: manufactured by Nippon Soda Co., Ltd.), and epoxy compounds having a silicone skeleton.

[0115] Examples of the (C) component containing an oxetane group include 1,4-bis(3-ethyl-3-oxetanylmethoxymethyl)benzene (e.g., OXT-121: manufactured by Toagosei Co., Ltd.), 3-ethyl-3-{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane (e.g., OXT-221: manufactured by Toagosei Co., Ltd.), 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl (e.g., ETERNACOLL OXBP: manufactured by UBE Corporation), bis[(3-ethyl-3-oxetanyl)methyl]isophthalate (e.g., ETERNACOLL OXIPA: manufactured by UBE Corporation), and the like.

[0116] Component (C) preferably contains at least one oxirane group, and more preferably contains at least two oxirane groups, which reacts efficiently with the alkali-soluble groups of component (A) to increase the crosslink density, which tends to improve the toughness and alkali resistance of the cured film.

[0117] The content of the (C) component is preferably 10% by mass to 100% by mass, and more preferably 15% by mass to 80% by mass, based on the total mass of the (A) component. By making it 10% by mass or more, a sufficient crosslinked structure can be formed, which makes it easier to increase the alkali resistance. Also, if it is 100% by mass or less, it is easier to adjust the crosslink density to an appropriate level, which makes it easier to maintain the toughness of the resin film.

[0118] 1-4.(D) Photopolymerization initiator The (D) photopolymerization initiator (hereinafter also referred to as "component (D)") is a compound that generates active species such as radicals, cations, and anions upon stimulation with light, and initiates a polymerization reaction. Photopolymerization initiators that generate radicals upon irradiation with light are preferred. The (D) component may contain a photosensitizer as necessary in addition to the compound that generates the active species.

[0119] When the resin film is exposed and developed to form a pattern, it is preferable that the curable resin composition contains the component (D). The unsaturated groups of the components (A) and (B) react with each other due to the active species generated from the photopolymerization initiator. This causes a difference in solubility in an alkaline developer or the like between the exposed and unexposed areas, making it possible to pattern the resin film.

[0120] Examples of the (D) component include oxime ester initiators, α-hydroxyacetophenone initiators, α-aminoacetophenone initiators, acylphosphine oxide initiators, and intramolecular hydrogen abstraction photopolymerization initiators. Among them, from the viewpoint of facilitating shortening the curing time of the curable resin composition, oxime ester initiators or α-aminoacetophenone initiators are preferred, and α-aminoacetophenone initiators are more preferred. As the (D) component, a commercially available product can be used.

[0121] Further, examples of the component (D) include the polymerization initiators described in paragraphs 0031 to 0042 of JP-A No. 2011-095716 and paragraphs 0064 to 0081 of JP-A No. 2015-014783.

[0122] Examples of aminoacetophenone initiators include 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad379EG, the Omnirad series is a product of IGM Resins BV), 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name: Omnirad 907), and APi-307 (1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one, manufactured by Shenzhen UV-ChemTech Ltd.).

[0123] Examples of the oxime ester-based initiator include O-oxime ester-based photopolymerization initiators represented by general formula (D-1) or general formula (D-2).

[0124] [ka]

[0125] In formula (D-1), R 61 , R 62 each independently represents an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 18 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 4 to 12 carbon atoms; R 63 represents an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms. Here, the alkyl group and the aryl group may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkanoyl group having 1 to 10 carbon atoms, or a halogen, and the alkylene portion may contain an unsaturated bond, an ether bond, a thioether bond, or an ester bond. The alkyl group may be any of linear, branched, and cyclic alkyl groups.

[0126] [ka]

[0127] In formula (D-2), R 64 and R 65 R are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, a cycloalkylalkyl group, or an alkylcycloalkyl group having 4 to 10 carbon atoms, or a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms. 66 are each independently a linear or branched alkyl or alkenyl group having 2 to 10 carbon atoms, and -CH 2 A part of the - groups may be replaced by -O- groups. 64 ~R 66 A part of the hydrogen atoms in the group may be substituted with halogen atoms.

[0128] Commercially available oxime ester initiators include, for example, 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] (trade name: IRGACURE OXE-01, IRGACURE series, manufactured by BASF), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF), [8-[5-(2,4,6-trimethylphenyl)-11-(2-ethylhexyl)-11H-benzo[a]carbazolyl][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methanone-(O-acetyloxime) (trade name: IRGACURE OXE-03, manufactured by BASF), and OXE-03, manufactured by BASF), 1-[4-[4-(2-benzofuranylcarbonyl)phenyl]thio]phenyl]-4-methylpentanone-1-(O-acetyloxime) (trade name: IRGACURE OXE-04, manufactured by BASF, and trade name: Lunar 6, DKSH Japan), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-305, Changzhou Strong Electronic New Materials Co., Ltd.), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H-carbazol-3-yl]-, 2-(O-acetyloxime) (trade name: TR-PBG-326, Changzhou Strong Electronic New Materials Co., Ltd.), and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino)hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (trade name: TR-PBG-391, Changzhou Strong Electronic New Materials Co., Ltd.).

[0129] Other examples of the (D) component include 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one (trade name: Omnirad 127), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (trade name: Omnirad 369), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (trade name: Omnirad 1173), 1-hydroxy-cyclohexyl-phenyl-ketone (trade name: Omnirad 184), 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name: Omnirad 651), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H) and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819).

[0130] Examples of the photosensitizer include acetophenones such as triethanolamine, triisopropanolamine, benzophenone, 4,4'-bisdimethylaminobenzophenone (Michler's ketone), 4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4,4'-diethylaminobenzophenone, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, and p-tert-butylacetophenone; benzoin ethers such as benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; 2-dimethylaminoethylbenzoic acid, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid (n-butoxy) ether, and the like. benzophenones such as ethyl, 4-dimethylaminobenzoate isoamyl, 4-dimethylaminobenzoate 2-ethylhexyl, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 4-benzoyl-4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, and 3,3'-dimethyl-4-methoxybenzophenone; thioxanthones such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone; aminobenzophenones such as 4,4'-bisdiethylaminobenzophenone; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, and camphorquinone. Among these, from the viewpoint of increasing the polymerization efficiency, it is preferable to use 4,4'-bisdimethylaminobenzophenone (Michler's ketone) or diethylthioxanthone, and 4,4'-bisdimethylaminobenzophenone (Michler's ketone) is more preferable.

[0131] The content of the photosensitizer is preferably 0.5% by mass to 400% by mass, and more preferably 1% by mass to 300% by mass, based on the total mass of the component (D). When the content of the photosensitizer is 0.5% by mass or more, the sensitivity of the photopolymerization initiator can be improved, making it easier to increase the rate of photopolymerization. When the content of the photosensitizer is 400% by mass or less, it is easier to suppress excessive increase in sensitivity.

[0132] The content of the (D) component is preferably 0.1% by mass to 30% by mass, more preferably 0.3% by mass to 20% by mass, based on the total mass of the (A) component and the (B) component. When the content of the photopolymerization initiator is 0.1% by mass, photopolymerization can be promoted, and the photopolymerization rate can be easily increased. When the content of the photopolymerization initiator is 30% by mass or less, excessive increase in sensitivity can be suppressed, and scorching, peeling residue, and the like can be prevented from occurring when ablation is performed by irradiating light.

[0133] 1-5.(E) Acrylic leveling agent Component (E) segregates on the coating surface and controls the viscosity and surface tension of the coating surface, thereby enhancing the surface smoothness of the resin film.

[0134] The component (E) is not particularly limited as long as it is composed of a (meth)acrylic polymer obtained mainly by polymerizing an acrylic monomer or a methacrylic monomer and has a weight average molecular weight of 3000 to 40000. In the present application, the acrylic leveling agent refers to a (meth)acrylic polymer that does not contain a perfluoroalkyl group. In the present specification, the weight average molecular weight (Mw) of the component (E) can be a styrene-equivalent value determined by gel permeation chromatography (GPC) (for example, "HLC-8220GPC" (manufactured by Tosoh Corporation)).

[0135] The "(meth)acrylic polymer" may include a polymer obtained by polymerizing only acrylic monomers, may include a polymer obtained by polymerizing only methacrylic monomers, or may include a polymer obtained by copolymerizing an acrylic monomer and a methacrylic monomer.

[0136] The weight average molecular weight of the (E) component is 3000 to 40000, and preferably 10000 to 40000. By making the weight average molecular weight 3000 or more, the surface segregation of the (E) component is likely to be enhanced, and the surface smoothness of the resin film is likely to be enhanced. By making the weight average molecular weight 10000 or more, the above effects are likely to be further enhanced, regardless of the weight average molecular weight of the (A) component. By further reducing the weight average molecular weight, the compatibility with the (A) component can be increased, and the haze can be made less likely to deteriorate.

[0137] In addition, the ratio [Mw(E)] / [Mw(A)] of the weight average molecular weight [Mw(E)] of the (E) component to the weight average molecular weight [Mw(A)] of the (A) component is preferably 0.5 to 12.0, more preferably 1.0 to 10.0, and even more preferably 1.0 to 7.0. The reason is not necessarily clear, but is considered as follows. If the weight average molecular weight of the (A) component is relatively small compared to the weight average molecular weight of the (E) component, the fluidity of the coating film is likely to increase, and the (E) component is likely to segregate on the surface of the coating film. In addition, by making the weight average molecular weight of the (E) component relatively large compared to the weight average molecular weight of the (A) component, phase separation between the (A) component and the (E) component is promoted, and the (E) component is likely to segregate on the surface of the coating film. If [Mw(E)] / [Mw(A)] is 0.5 or more, the segregation property of the (E) component can be increased to cause it to be unevenly distributed on the surface of the coating film, and the surface smoothness can be easily improved. When [Mw(E)] / [Mw(A)] is 12.0 or less, compatibility with the component (A) is easily improved, and deterioration of haze can be suppressed.

[0138] Examples of the (E) component include polymers obtained by polymerizing (meth)acrylic acid alkyl esters, etc. Examples of the (meth)acrylic acid alkyl esters include (meth)acrylic acid ethyl ester, (meth)acrylic acid n-propyl ester, (meth)acrylic acid isopropyl ester, (meth)acrylic acid n-butyl ester, (meth)acrylic acid isobutyl ester, (meth)acrylic acid t-butyl ester, (meth)acrylic acid n-octyl ester, (meth)acrylic acid 2-ethylhexyl ester, (meth)acrylic acid isononyl ester, etc.

[0139] Commercially available products of component (E) include Polyflow No. 90, Polyflow No. 95, and Polyflow No. 99C (all manufactured by Kyoeisha Chemical Industry Co., Ltd.).

[0140] (E) Polar term δ of Hansen solubility parameter of component P But 4.0MPa 1 / 2 ~10.0MPa 1 / 2 Preferably, the pressure is 6.0 MPa. 1 / 2 ~10.0MPa 1 / 2 It is more preferable that the above formula is used. The reason for this is not entirely clear, but it is believed to be as follows. Alkali-soluble resins tend to have high polarity due to the high polarity of the alkali-soluble groups. On the other hand, highly hydrophobic sites are sometimes introduced into acrylic leveling agents in order to enhance surface segregation. Since such hydrophobic sites are often low in polarity, acrylic leveling agents often have low polarity. For this reason, it has been difficult to achieve both surface segregation and compatibility of acrylic leveling agents used with alkali-soluble resins. Therefore, δ P It is believed that by appropriately increasing the δ of component (E), compatibility with alkali-soluble resins is easily improved. P is 4.0MPa 1 / 2 If the δ of the component (E) is not less than 1, the compatibility with the component (A), which has a relatively high polarity, is improved, and the haze of the resin film can be easily reduced. P is 10.0MPa 1 / 2When it is equal to or less than this, the polarity of the component (E) can be appropriately reduced, making it easier to enhance the surface smoothness even in a resin film containing the component (A).

[0141] The Hansen solubility parameter is expressed by three parameters: the dispersion force term, the dipole interaction term, and the hydrogen bond term. The dispersion force term in the Hansen solubility parameter of the solvent or component (E) is expressed as δ D , the dipole interaction term is δ P , hydrogen bond term δ H This is expressed as follows.

[0142] The Hansen solubility parameter of component (E) is determined as follows. First, when component (E) is mixed with a plurality of solvents whose Hansen solubility parameters (dispersion force term, dipole interaction term, and hydrogen bond term) are known, the solvents in which component (E) is dissolved (good solvents) and the solvents in which component (E) is not dissolved (poor solvents) are identified. Then, using HSPiP (Hansen Solubility Parameters in Practice), a program for determining Hansen solubility parameters, the Hansen solubility parameters of each solvent are plotted in Hansen space to set the smallest virtual sphere (Hansen's solubility sphere) in which good solvents are included inside and poor solvents are included outside, and the central coordinates of the Hansen solubility sphere are taken as the Hansen solubility parameter of component (E).

[0143] The Hansen solubility parameter of the component (E) can also be calculated by a known method from the chemical structure and amount of each component (E).

[0144] The content of the (E) component is preferably 0.10% by mass to 0.90% by mass, more preferably 0.30% by mass to 0.80% by mass, based on the total mass of the solid content of the curable resin composition. When the (E) component is 0.10% by mass or more, the coating surface can be sufficiently covered, making it easier to improve surface smoothness. When the (E) component is 0.90% by mass or less, the compatibility with the (A) component can be improved, making it difficult for the haze to deteriorate.

[0145] 1-6.(F) Solvent The component (F) adjusts the viscosity of the photosensitive resin composition and improves the coatability.

[0146] Component (F) may be any of the following: alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, 3-hydroxy-2-butanone, diacetone alcohol, etc.; terpenes such as α- or β-terpineol, ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, cyclopentanone, N-methyl-2-pyrrolidone, etc.; aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, etc.; cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, etc. Examples of the solvent include glycol ethers such as propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether, and esters such as ethyl acetate, butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-3-butyl acetate, 3-methoxy-3-methyl-1-butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. By dissolving and mixing using these, a uniform solution-like composition can be obtained. Among these solvents, esters are preferred, and propylene glycol monomethyl acetate is more preferred.

[0147] The amount of the solvent varies depending on the target viscosity, but is preferably 45 to 90 mass % of the total mass of the curable resin composition in order to easily impart suitable coating suitability.

[0148] 1-7.Other additives The curable resin composition according to the present embodiment may contain additives such as a curing agent, a curing accelerator, a thermal polymerization inhibitor, an antioxidant, a plasticizer, a filler, a defoaming agent, a coupling agent, etc., as necessary. In addition, the curable resin composition may contain an ultraviolet absorbing agent or a pigment for increasing the absorbency of irradiated light.

[0149] Examples of curing agents include amine compounds, polyvalent carboxylic acid compounds, phenolic resins, amino resins, dicyandiamide, Lewis acid complex compounds, etc., which contribute to the curing of epoxy resins. Examples of curing accelerators include tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, boric acid esters, Lewis acids, organometallic compounds, imidazoles, etc., which contribute to the curing acceleration of epoxy resins. Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, hindered phenol compounds, etc. Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc. Examples of fillers include glass fiber, silica, mica, alumina, etc. Examples of coupling agents include 3-(glycidyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, and the like.

[0150] 2.Resin film The resin film according to this embodiment is formed from the above-mentioned curable resin composition.

[0151] The resin film is formed at least through a solvent drying step (pre-baking) described later. After the solvent drying step, the resin film may be photopolymerized through an exposure step, patterned through a development step, or thermally polymerized through a heat treatment step (post-baking). Among the resin films, the one before the heat treatment under the preferred heat treatment conditions (temperature, time) for advancing the crosslinking reaction in the "2-3. Step of Heating the Resin Film" described later is also called the "coating film" of the curable resin composition. The one after the heat treatment under the preferred heat treatment conditions (temperature, time) for advancing the crosslinking reaction described later is also called the "cured film" of the curable resin composition.

[0152] 2-1. Process of forming resin film The resin film forming step is a step of applying the curable resin composition to the surface of a support and / or an adherend to form a resin film containing the curable resin composition.

[0153] Examples of the method for applying the curable resin composition include known methods such as immersion in a solution, spin coating, ink jetting, spraying, and methods using a roller coater, land coater, slit coater, or spinner.

[0154] After the curable resin composition is applied by the above application method, the solvent is dried (prebaked) to form a coating film. Note that prebaking is performed by heating using an oven, a hot plate, etc. The heating temperature and heating time in prebaking are appropriately selected depending on the solvent used, and for example, prebaking is performed at a temperature of 60 to 110°C for 1 to 10 minutes.

[0155] The thickness of the resin film can be selected as desired. The thickness of the resin film according to this embodiment is preferably 1 μm to 50 μm, and more preferably 3 μm to 30 μm.

[0156] 2-2. Resin film exposure and development process The resin film exposure and development process may include at least an exposure process, but may not include a development process. In the exposure process, the resin film is irradiated with light, component (D) is photoreacted, and components containing unsaturated groups such as components (A) and (B) are photopolymerized. In this process, a part of the resin film may be irradiated with light through a photomask to photoreact a part of the resin film, and the resin film may be patterned in the development process. Alternatively, the entire surface of the resin film may be irradiated with light to photoreact the entire resin film.

[0157] Examples of light used in the exposure step include visible light, ultraviolet light, far ultraviolet light, electron beams, X-rays, and the like. Among the above-mentioned light, ultraviolet light (wavelength 250 to 400 nm) is preferred. In addition, in the development step, a developer suitable for alkaline development is used. Examples of the developer include aqueous solutions of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, and the like. These developers can be appropriately selected according to the characteristics of the resin layer, and a surfactant may be added as necessary. The development temperature is preferably 20 to 35°C, and fine images can be precisely formed using a commercially available developing machine, ultrasonic cleaner, or the like. After the alkaline development, the film is usually washed with water. As the development treatment method, a shower development method, a spray development method, a dip (immersion) development method, a puddle (liquid puddle) development method, and the like can be applied.

[0158] 2-3. Process of heat treating the resin film In the process of heat treating the resin film, the polymerizable unsaturated groups of the (A) and (B) components react with each other, and the reaction between the acidic group of the (A) component and the epoxy group of the (C) component progresses. As the reaction progresses, a strong crosslinked structure can be formed, and the solvent resistance of the resin film can be further improved.

[0159] The heat treatment temperature for promoting the crosslinking reaction is preferably 150°C to 250°C, more preferably 180°C to 230°C. The heat treatment time is preferably 10 minutes to 120 minutes, more preferably 30 minutes to 90 minutes. By setting the treatment temperature to 150°C or higher and the treatment time to 10 minutes or longer, the crosslinking reaction proceeds well, and the solvent resistance of the adhesive layer can be easily increased. By setting the treatment temperature to 250°C or lower and the treatment time to 120 minutes or shorter, unintended side reactions do not occur, and coloring of the cured film and a decrease in adhesive strength can be easily suppressed.

[0160] 3.Laminate The laminate according to this embodiment includes a support, an adherend, and an adhesive layer disposed between the support and the adherend, the adhesive layer including a resin film of the curable resin composition described above.

[0161] The laminate according to this embodiment can also be suitably used as a substrate for patterning using a resist material, and a resist layer or a material layer may be disposed on the side of the adherend opposite the side in contact with the adhesive layer.

[0162] Here, the material layer is not particularly limited as long as it is a layer that can be patterned using a resist material. The material layer includes metal films and semiconductor films used in semiconductor elements, wiring, terminals, etc. included in electronic devices. The material layer may be a patterned layer or an unpatterned layer. When the material layer is composed of two or more layers, all layers may be unpatterned layers, some layers may be patterned and the rest may be unpatterned layers, or all layers may be patterned layers.

[0163] For example, when the material layer is patterned by an etching process, the resist layer may be disposed so as to sandwich the material layer between the resist layer and the adherend. In this case, the material layer preferably includes an unpatterned layer, and when the material layer is composed of two or more layers, it is preferable that at least one layer is an unpatterned layer. When simply forming a concave-convex pattern on a substrate or when patterning the material layer by a lift-off process, the resist layer may be disposed in contact with the adherend.

[0164] The laminate according to the present embodiment may also include a patterned material layer disposed on the surface of the adherend opposite to the surface on which the adhesive layer is disposed. When the material layer is composed of two or more layers, it is sufficient that at least one layer is patterned, and an unpatterned layer may also be included.

[0165] 3-1.Support There are no limitations on the type of support, so long as an adhesive layer can be formed on the surface thereof.

[0166] In this embodiment, the support is preferably laser transmissive. In particular, the support is more preferably transmissive to light (laser) having a wavelength of 10 nm to 400 nm, and even more preferably transmissive to light (laser) having a wavelength of 100 nm to 400 nm. Examples of the support having the laser transmissive property include a glass substrate, an acrylic substrate, a sapphire substrate, and a quartz substrate. However, for the glass substrate and the acrylic substrate, it is necessary to use a substrate having a composition that has a sufficient transmittance of the wavelength of the light to be used. Of the above supports, a glass substrate is preferable.

[0167] 3-2.Adherent Examples of the adherend include a semiconductor wafer, a semiconductor chip, a light-emitting element, an optical glass wafer, a metal foil, a polishing pad, a resin coating film, a wiring layer, etc. The adherend may be a single layer, or may have a multilayer structure of two or more layers, and may include a patterned layer in some layers. When used as a substrate for patterning using a resist material, the adherend preferably includes a semiconductor wafer.

[0168] In addition, the adherend may have an uneven pattern formed on the surface opposite to the surface in contact with the adhesive layer.

[0169] 3-3.Adhesive layer The adhesive layer is formed by applying the above-mentioned curable resin composition to the surface of a support and / or an adherend, and then undergoing at least a step of drying off the solvent.

[0170] 3-4.Resist layer The components used in the resist layer may be any known material. The components used in the resist layer are not particularly limited as long as they can be patterned in the developing step described below and can be peeled off in the peeling step. The resist layer may be a positive resist layer or a negative resist layer.

[0171] Moreover, as the resist layer forming material, commercially available liquid resist layer forming materials and dry film resists can also be used.

[0172] 3-5.Material layer The material layer may be a single layer, or may have a multi-layer structure of two or more layers.

[0173] The material layer may be made of any known material, including silicon materials such as silicon oxide, silicon nitride, and silicon oxynitride, and metal materials such as metal oxide.

[0174] 4. Manufacturing method of laminate The method for producing a laminate according to this embodiment includes the steps of: i) forming an adhesive layer containing the above-mentioned curable resin composition on a surface of either or both of a support and an adherend; and ii) adhering the support and the adherend via the formed adhesive layer.

[0175] The method for producing the laminate may also include a step of exposing and developing the adhesive layer, and a step of applying a resist layer.

[0176] Each step will be described below.

[0177] 4-1. Step of forming adhesive layer The adhesive layer forming step can be performed using the same method as in "2-1. Step of forming a resin film" above.

[0178] 4-2. Exposure and development process of adhesive layer The steps of exposing and developing the adhesive layer can be performed using the same method as in "2-2. Steps of exposing and developing the resin film" above.

[0179] 4-3. Step of bonding the support and the adherend The step of adhering the support and the adherend is a step of adhering the support and the adherend via the adhesive layer.

[0180] As a method for bonding the support and the adherend, for example, there is a method of contacting the adherend (wherein the adhesive is applied to the surface that contacts the adhesive layer) with the surface of the adhesive layer formed on the surface of the support and pressurizing the adherend while heating it. In addition, as for the bonding conditions between the support and the adherend, the temperature during pressurization is preferably from room temperature to 200°C or less, more preferably from 30°C to 150°C. The pressure during bonding is preferably from 0.01MPa to 20MPa, more preferably from 0.03MPa to 15MPa. In addition, if necessary, after completion of the pressurized thermocompression bonding, the bond can be thermally cured at a temperature of 120°C to 250°C. By bonding the support and the adherend under the above conditions, the adherend is more firmly fixed to the surface of the support via the adhesive layer.

[0181] In the bonding step, the support and the adherend may be bonded by photocuring. An example of a method for photocuring the adhesive layer is a method of irradiating light using a high-pressure mercury lamp. The bonding conditions for the support and the adherend are preferably such that the wavelength of the irradiated light is 200 to 500 nm. The exposure dose of the irradiated light is 25 mJ / cm. 2 ~3000mJ / cm 2 and preferably 50 mJ / cm 2 ~2000mJ / cm 2 It is more preferable that:

[0182] In this manner, the laminate of the present embodiment is formed.

[0183] The laminate can be separated into the support and the adherend by irradiating the adhesive layer from the support side with a laser having a wavelength of 10 nm to 400 nm, as described below.

[0184] 5. Processing method of laminate The method for treating a laminate according to the present embodiment includes the steps of (1) preparing the laminate described above, and (2) irradiating the laminate with light to separate the support and the adherend. Each step will be described below.

[0185] 5-1. Step of preparing laminate The step of preparing a laminate is a step of forming a laminate as described above, or of preparing an already formed laminate.

[0186] 5-2. Step of separating the support and the adherend The step of separating the support and the adherend is a step of separating the support and the adherend by irradiating the adhesive layer with light.

[0187] The light to be irradiated is not particularly limited as long as it can separate the support and the adherend. In this embodiment, the light is preferably ultraviolet light, and the wavelength of the ultraviolet light is more preferably 10 nm to 400 nm, and even more preferably 100 nm to 400 nm. If the wavelength of the ultraviolet light is 10 nm or more, the polymer, which is a component of the adhesive layer, absorbs the light and changes its quality, reducing the strength and adhesive force, so that the support and the adherend can be easily separated. In addition, if the wavelength is 400 nm or less, the adhesive layer in the processed portion absorbs the light, so that the generation of residue of the cured film can be suppressed.

[0188] Examples of the ultraviolet light source include a low mercury lamp, a high pressure mercury lamp, an extra-high pressure mercury lamp, a metal halide lamp, a far ultraviolet light laser, etc. Among the above light sources, a laser is preferable.

[0189] Examples of the laser include solid-state lasers, liquid lasers, and gas lasers. Examples of the solid-state laser include semiconductor pumped lasers. Examples of the liquid laser include dye lasers. Examples of the gas laser include excimer lasers. Among the lasers, semiconductor pumped lasers are preferred.

[0190] Examples of the semiconductor pumped laser include Nd:YAG laser, Nd:YLF laser, Nd:glass laser, Nd:YVO4 laser, Yb:YAG laser, Yb-doped fiber laser, Er:YAG laser, Tm:YAG laser, etc. Examples of the excimer laser include KrF laser, XeCl laser, ArF laser, F2 laser, etc. Among the above lasers, the Nd:YAG laser is preferred.

[0191] The output and cumulative light quantity of the light irradiated onto the adhesive layer vary depending on the type of light source, etc., but when the irradiated light is a laser, the output can be 0.1 mW to 200 W. The cumulative light quantity can be 1 mJ / cm2. 2 ~50J / cm 2It is preferable that the integrated light amount is 0.1 mJ / cm 2 If the intensity is more than 50 J / cm, burning and peeling residue are less likely to occur during ablation. 2 If the ablation speed is equal to or less than this, the ablation speed can be appropriately controlled to perform appropriate processing.

[0192] As a method of irradiating the adhesive layer with light (laser), it is preferable to irradiate the entire surface of the adhesive layer with a laser from the support side. The method of irradiating the laser is not particularly limited, and can be performed by a known method.

[0193] The laminate is capable of separating the support and the adherend by irradiating the adhesive layer with light (laser).

[0194] The method for treating a laminate according to this embodiment may include a step of processing the prepared laminate prior to the step of separating the support and the adherend.

[0195] Methods for processing the laminate include thinning of adherends such as dicing and back grinding, photofabrication, stacking of semiconductor chips, mounting of various elements, resin sealing, and the like.

[0196] The method for treating a laminate according to the present embodiment may further include a step of transferring the processed laminate from one device to another. A method for transferring the laminate includes using a robot arm or the like.

[0197] 6.Semiconductor Package The semiconductor package according to this embodiment includes the above-mentioned resin film as an insulating film.

[0198] The resin film according to the present embodiment can be used as an insulating film for printed wiring boards and semiconductor packages, for example, resist layers such as solder resist layers, plating resist layers, and etching resist layers, and interlayer insulating layers for multi-layer printed wiring boards. In this specification, the term "semiconductor package" refers to a package including a semiconductor chip and a package in a form that can be mounted on a printed board, such as a flip chip package stacked on an interposer, in addition to a flip chip package and a wafer level package. In particular, the resin film is useful for an optical semiconductor package combined with a light emitting element (preferably an LED such as a UV-LED or a Blue-LED).

[0199] 7.Display device The display device according to this embodiment includes the above-mentioned resin film as an insulating film or a protective film.

[0200] The display device according to the present embodiment can be used as an insulating film in various display devices such as a liquid crystal display, an organic EL display device, a μLED display device, and a display device to which quantum dots are applied. The display device according to the present embodiment may have a semiconductor package including the above-mentioned resin film as an insulating film.

[0201] 8.Other uses The resin film according to this embodiment may be used as a protective layer in various display devices, a gas barrier film, a lens, a sealing material for semiconductor light-emitting elements such as light-emitting diodes (LEDs), a top coat for paints or inks, a hard coat for plastics, an anti-rust film for metals, and the like. EXAMPLES

[0202] Hereinafter, the embodiments of the present invention will be described in detail based on examples and comparative examples, but the present invention is not limited to these.

[0203] First, synthesis examples of the unsaturated group-containing polymerizable resin, component (A), will be described. Unless otherwise specified, the resins in these synthesis examples were evaluated as follows.

[0204] In addition, when the same model of measuring equipment is used, the name of the equipment manufacturer is omitted from the second place. In addition, in the examples, all glass substrates used to prepare the substrates with cured films for measurement are used after the same treatment. In addition, when the first decimal place of the content of each component is 0, the notation after the decimal point may be omitted.

[0205] [Solid content concentration] 1 g of the resin solution obtained in the synthesis example was poured into a glass filter (weight: W 0 (g)] and weighed [W 1 (g)], and the weight after heating at 160°C for 2 hours [W 2 (g)] was calculated using the following formula: Solid content concentration (wt%)=100×(W 2 -W 0 ) / (W 1 -W 0 )

[0206] [Acid value] The resin solution was dissolved in dioxane and titrated with a 1 / 10N KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.) to determine the content.

[0207] [Molecular weight] Measurement was performed using gel permeation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, columns: TSKgelSuper H-2000 (2 tubes) + TSKgelSuper H-3000 (1 tube) + TSKgelSuper H-4000 (1 tube) + TSKgelSuper H-5000 (1 tube) (manufactured by Tosoh Corporation), temperature: 40°C, rate: 0.6 ml / min), and the weight average molecular weight (Mw) was calculated as a value converted into standard polystyrene (manufactured by Tosoh Corporation, PS-oligomer kit).

[0208] [Hansen solubility parameters] Component (E) was mixed into 24 different solvents to a concentration of 0.01 g / mL, and its solubility / insolubility in each solvent was evaluated. The results were then entered into "Hansen Solubility Parameters in Practice (HSPiP)" to create a Hansen solubility sphere, and the central coordinates of the Hansen solubility sphere were used as the Hansen solubility parameter for component (E).

[0209] [Solvents for evaluating Hansen solubility parameters] Acetone: (δ D δ P δ H )=(15.5 10.4 7.0) Diacetone alcohol: (δ D δ P δ H )=(15.8 8.2 10.8) Ethanol: (δ D δ P δ H )=(15.8 8.8 19.4) γ-Butyl lactone: (δ D δ P δ H )=(18.0 16.6 7.4) N-Methyl-2-pyrrolidone: (δ D δ P δ H )=(18.0 12.3 7.2) Propylene glycol monomethyl ether: (δ D δ P δ H )=(15.6 6.3 11.6) Propylene glycol monomethyl ether acetate: (δ D δ P δ H )=(15.6 5.6 9.8) Propylene glycol diacetate: (δ D δ P δ H )=(15.6 5.6 7.8) Toluene: (δ D δ P δ H)=(18.0 1.4 2.0) 1-Butanol: (δ D δ P δ H )=(16.0 5.7 15.8) 2-Phenoxyethanol: (δ D δ P δ H )=(17.8 5.7 14.3) Cyclohexanol: (δ D δ P δ H )=(17.4 4.1 13.5) Diethylene glycol: (δ D δ P δ H )=(16.6 12.0 19.0) Dimethylformamide: (δ D δ P δ H )=(17.4 13.7 11.3) Dimethyl sulfoxide: (δ D δ P δ H )=(18.4 16.4 10.2) Dipropylene glycol: (δ D δ P δ H )=(16.5 10.6 17.7) Methyl isobutyl ketone: (δ D δ P δ H )=(15.3 6.1 4.1) Dichloromethane: (δ D δ P δ H )=(17.0 7.3 7.1) Butyl acetate: (δ D δ P δ H )=(15.8 3.7 6.3) Propylene carbonate: (δ D δ P δ H )=(20.0 18.0 4.1) Tetrachloroethylene: (δ D δ P δH )=(18.3 5.7 0.0) Methanol: (δ D δ P δ H )=(14.7 12.3 22.3) Acetonitrile: (δ D δ P δ H )=(15.3 18.0 6.1) Hexane: (δ D δ P δ H )=(14.9 0.0 0.0) δ D , δ P , δ H The units are all MPa. 1 / 2 In this case, the units are omitted.

[0210] The abbreviations used in the Synthesis Examples are as follows. BPFE: Bisphenol fluorene type epoxy resin (epoxy resin with general formula (X1) where Ar is a benzene ring and l is 0, epoxy equivalent 256g / eq) [ka] AA: Acrylic acid TPP: Triphenylphosphine PGMEA: Propylene glycol monomethyl ether acetate BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride THPA: 1,2,3,6-Tetrahydrophthalic anhydride GMA: Glycidyl methacrylate RUVA-93: 2-(2'-hydroxy-5'-methacryloyloxyethylphenyl)-2-H-benzotriazole (Otsuka Chemical Co., Ltd.) MMA: Methyl methacrylate MA: methacrylic acid HEMA: 2-hydroxyethyl methacrylate ADVN: 2,2'-azobis(2,4-dimethylvaleronitrile) MOI: 2-isocyanatoethyl methacrylate

[0211] [Synthesis Example 1] In a 250 mL four-neck flask equipped with a reflux condenser, BPFE (50.00 g, 0.10 mol), AA (14.41 g, 0.20 mol), TPP (0.26 g), and PGMEA (15.00 g) were charged and stirred at 100 to 105° C. for 12 hours to obtain a reaction product. Thereafter, PGMEA (49.60 g) was added to the reaction product, and the solid content was adjusted to 50 mass%.

[0212] Next, BPDA (14.77 g, 0.06 mol) and THPA (7.64 g, 0.05 mol) were added to the obtained reaction product, and the mixture was stirred at 115 to 120° C. for 6 hours to obtain an unsaturated group-containing alkali-soluble resin (A)-1. The solid content of the obtained resin solution was 57.4 mass%, the acid value (solid content equivalent) was 96 mg KOH / g, and the Mw by GPC analysis was 3600.

[0213] [Synthesis Example 2] In a 250 mL four-neck flask equipped with a reflux condenser, the unsaturated group-containing alkali-soluble resin (A)-1 (151.68 g) obtained in Synthesis Example 1, GMA (5.35 g, 0.04 mol), and TPP (0.10 g) were charged and stirred at 100 to 105° C. for 8 hours to obtain an unsaturated group-containing curable resin (A)-2. The solid content concentration of the obtained resin solution was 58.9 mass%, the acid value (solid content equivalent) was 69 mgKOH / g, and the Mw by GPC analysis was 4000.

[0214] [Synthesis Example 3] In a 250 mL four-neck flask equipped with a reflux condenser, the unsaturated group-containing alkali-soluble resin (A)-1 (151.68 g) obtained in Synthesis Example 1, GMA (10.71 g, 0.08 mol), and TPP (0.20 g) were charged and stirred at 100 to 105° C. for 8 hours to obtain an unsaturated group-containing curable resin (A)-3. The solid content concentration of the obtained resin solution was 60.3 mass%, the acid value (solid content equivalent) was 43 mgKOH / g, and the Mw by GPC analysis was 4700.

[0215] [Synthesis Example 4] In a 250 mL four-neck flask equipped with a reflux condenser, the unsaturated group-containing alkali-soluble resin (A)-1 (151.68 g) obtained in Synthesis Example 1, GMA (16.06 g, 0.11 mol), and TPP (0.30 g) were charged and stirred at 100 to 105° C. for 8 hours to obtain an unsaturated group-containing curable resin (A)-4. The solid content concentration of the obtained resin solution was 61.6 mass%, the acid value (solid content equivalent) was 20 mgKOH / g, and the Mw by GPC analysis was 5,300.

[0216] [Synthesis Example 5] In a 250 mL four-neck flask equipped with a reflux condenser, BPFE (50.00 g, 0.10 mol), AA (14.41 g, 0.20 mol), TPP (0.26 g), and PGMEA (15.00 g) were charged and stirred at 100 to 105° C. for 12 hours to obtain a reaction product. Thereafter, PGMEA (49.60 g) was added to the reaction product, and the solid content was adjusted to 50 mass%.

[0217] Next, BPDA (20.68 g, 0.07 mol) and THPA (0.31 g, 0.002 mol) were added to the obtained reaction product, and the mixture was stirred at 115 to 120° C. for 6 hours to obtain an unsaturated group-containing alkali-soluble resin (A)-5. The solid content concentration of the obtained resin solution was 57.0 mass%, the acid value (solid content equivalent) was 92 mg KOH / g, and the Mw by GPC analysis was 6700.

[0218] [Synthesis Example 6] In a reactor equipped with a temperature controller, stirrer, reflux condenser, and nitrogen gas inlet tube, 233 parts by mass of PGMEA as a solvent, 59 parts by mass (0.18 mol) of RUVA-93 as an unsaturated monomer containing an ultraviolet absorbing group, 16 parts by mass (0.16 mol) of MMA and 9.0 parts by mass (0.10 mol) of MA as another unsaturated monomer, and 15 parts by mass (0.12 mol) of HEMA were added and heated to 80 ° C, and then replaced with nitrogen. 2 parts by mass of ADVN were added as a polymerization initiator and reacted for 1 hour. Then, 0.5 parts by mass of ADVN were added, heated to 90 ° C, and aged for 3 hours to synthesize an ultraviolet absorbing copolymer. The molar absorption coefficient of RUVA-93 at a wavelength of 355 nm was 17,000 L / (mol cm). The molar absorption coefficient can be calculated by measuring the absorbance of a 0.001 wt% acetonitrile solution in a quartz cell with an optical path length of 1 cm using an ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Corporation), and then dividing the absorbance by the molar concentration.

[0219] To this, 18 parts by mass of MOI (0.12 mol), 0.01 parts by mass of a tin compound as a catalyst, and 0.04 parts by mass of methoquinone as a polymerization inhibitor were added, and the MOI addition reaction to the ultraviolet absorbing copolymer was carried out at 60°C for about 6 hours. The end point of the reaction was confirmed by the disappearance of the isocyanate peak from FT-IR. After the reaction was completed, PGMEA was added to this to adjust the solid content to 30.0% by mass, and the present invention product (A)-6 was obtained. The acid value (solid content equivalent) of the obtained resin solution was 56 mgKOH / g, and the Mw by GPC analysis was 29,000.

[0220] Curable resin compositions were prepared in the amounts (unit: mass %) shown in Tables 1 and 2. The components used in Tables 1 and 2 are as follows.

[0221] (Alkali-soluble resin containing unsaturated groups) (A)-1: Resin solution obtained in Synthesis Example 1 (solid content concentration: 57.4% by mass) (A)-2: Resin solution obtained in Synthesis Example 2 (solid content concentration: 58.9% by mass) (A)-3: Resin solution obtained in Synthesis Example 3 (solid content concentration: 60.3% by mass) (A)-4: Resin solution obtained in Synthesis Example 4 (solid content concentration: 61.6% by mass) (A)-5: Resin solution obtained in Synthesis Example 5 (solid content concentration: 57.0% by mass) (A)-6: Resin solution obtained in Synthesis Example 6 (solid content concentration: 30.0% by mass)

[0222] (Polymerizable monomer) (B)-1: Mixture of dipentaerythritol pentaacrylate and hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.)

[0223] (Oxirane Compounds) (C)-1: Biphenyl-type epoxy resin (jER YX4000, manufactured by Mitsubishi Chemical Corporation; "jER" is a registered trademark of the company; epoxy equivalent: 190 g / eq)

[0224] (Photopolymerization initiator) (D)-1: 2-[4-(methylthio)benzoyl]-2-(4-morpholinyl)propane (Omnirad907, manufactured by IGM Resins BV, "Omnirad" is a registered trademark of the company) (D)-2: Michler's ketone

[0225] (Acrylic leveling agent) (E)-1: Polyflow No. 90 (manufactured by Kyoeisha Chemical Co., Ltd., Mw is 17,800 by GPC analysis, polarity term δ of Hansen solubility parameter P is 3.5MPa 1 / 2 ) (E)-2: Polyflow No. 95 (manufactured by Kyoeisha Chemical Co., Ltd., Mw is 21,300 by GPC analysis, polarity term δ of Hansen solubility parameter P is 7.5MPa 1 / 2 ) (E)-3: Polyflow No. 99C (manufactured by Kyoeisha Chemical Co., Ltd., Mw is 7500 by GPC analysis, polarity term δ of Hansen solubility parameter P is 3.5MPa 1 / 2 ) (E)-4: Polyflow No. 75 (manufactured by Kyoeisha Chemical Co., Ltd., Mw is 2100 by GPC analysis, polarity term δ of Hansen solubility parameter P is 7.6MPa 1 / 2 ) (E)-5: Polyflow No. 77 (manufactured by Kyoeisha Chemical Co., Ltd., Mw is 2000 by GPC analysis, polarity term δ of Hansen solubility parameter P is 8.8MPa 1 / 2 )

[0226] (solvent) (F)-1: Propylene glycol monomethyl ether acetate (PGMEA)

[0227] [Table 1]

[0228] [Table 2]

[0229] [evaluation] The curable resin compositions shown in Tables 1 and 2 were evaluated as follows.

[0230] [Surface smoothness evaluation] (Preparation of substrate for surface smoothness evaluation) The curable resin compositions shown in Tables 1 and 2 were applied onto a 5-inch silicon wafer using a spin coater so that the film thickness after drying would be 5.0 μm, and the wafer was prebaked at 100° C. for 5 minutes using a hot plate to produce a coating film. Next, an i-line illuminance of 30 mW / cm was applied to the dried film. 2 100mJ / cm2 ultra-high pressure mercury lamp 2 Finally, the coating was post-baked at 230° C. for 30 minutes using a hot air dryer to obtain substrates with cured films according to Examples 1-14 and Comparative Examples 1-4.

[0231] (Evaluation method) After the main curing (post-baking), the maximum surface irregularity was measured in a measurement area of ​​230 μm square using a non-contact three-dimensional optical interference microscope "WYKO Contour-GT" (manufactured by Bruker Japan). A rating of △ or higher was considered to be a pass.

[0232] The maximum value of the surface unevenness in the surface smoothness evaluation was calculated from the following formula, where the maximum value of the film thickness in the measurement range was defined as L1 and the minimum value was defined as L2. Maximum surface roughness (nm) = L1-L2

[0233] (Evaluation Criteria) ◎: The maximum surface irregularity is 20 nm or less ○: The maximum surface irregularity is more than 20 nm and 30 nm or less. △: The maximum surface irregularity is more than 30 nm and 50 nm or less. ×: The maximum value of the surface irregularities exceeds 50 nm.

[0234] [Developability evaluation] (Preparation of substrate with cured film for evaluating developability) The curable resin compositions shown in Tables 1 and 2 were applied onto a glass substrate "#1737" using a spin coater so that the film thickness after heat curing treatment would be 4.0 μm, and the substrate was prebaked at 100° C. for 5 minutes using a hot plate to prepare a coating film. Next, the dried film was coated with an i-line illuminance of 30 mW / cm 2 100mJ / cm2 ultra-high pressure mercury lamp 2 The dried film was exposed to ultraviolet light of 1000 ohms to cause a photocuring reaction.

[0235] The exposed film was then developed at 1 kgf / cm with a 2.38% TMAH (tetramethylammonium hydroxide) developer at 23°C. 2 After developing for 60 seconds with a shower pressure of 5kgf / cm 2 The unexposed areas were removed by spray washing with water to form a line and space pattern. Finally, the coating was post-cured (post-baked) at 230° C. for 30 minutes using a hot air dryer to obtain a substrate with a cured film for evaluating developability.

[0236] (Evaluation method) The line and space patterns (50 μm / 50 μm, 30 μm / 30 μm) of the cured film on the obtained substrate with the cured film were observed using an optical microscope to judge the presence or absence of residues in the space areas (unexposed areas).

[0237] (Evaluation Criteria) ○: No residue was observed in the spaces for both the 50μm / 50μm and 30μm / 30μm patterns. △: No residue was observed in the 50μm / 50μm pattern, but residue was observed in the space of the 30μm / 30μm pattern. ×: Residue is observed in the space area for both 50μm / 50μm and 30μm / 30μm patterns.

[0238] [Compatibility evaluation] (Preparation of substrate for compatibility evaluation) The curable resin compositions shown in Tables 1 and 2 were applied to a glass substrate "#1737" using a spin coater so that the film thickness after drying would be 5.0 μm, and the substrate was prebaked at 100° C. for 5 minutes using a hot plate to prepare a coating film. Next, an i-line illuminance of 30 mW / cm was applied to the dried film. 2 100mJ / cm2 ultra-high pressure mercury lamp 2 Finally, the coating was post-baked at 230° C. for 30 minutes using a hot air dryer to obtain substrates with cured films according to Examples 1-14 and Comparative Examples 1-4.

[0239] (Evaluation method) The haze value of the substrate with the cured film was measured using a turbidity meter "NDH5000" (manufactured by Nippon Denshoku Industries Co., Ltd.) A rating of △ or higher was deemed to be acceptable.

[0240] (Evaluation Criteria) ○: The haze value of the substrate with the cured film is 10% or less. △: The haze value of the substrate with the cured film is more than 10% and 20% or less. ×: The haze value of the substrate with the cured film is more than 20%.

[0241] The evaluation results are shown in Tables 3 and 4.

[0242] [Table 3]

[0243] [Table 4]

[0244] As is apparent from Tables 3 and 4, in a curable resin composition containing component (A) having an acid value of 25 to 200 mgKOH / g and component (E) having a weight average molecular weight of 3,000 to 40,000, it is possible to achieve both surface smoothness and alkaline developability of the cured film.

[0245] As can be seen from a comparison of Examples 1 to 9, by setting the molecular weight ratio of component (A) to component (E) [Mw(E)] / [Mw(A)] to 0.5 to 12.0, component (E) can be effectively segregated on the coating film surface, thereby improving surface smoothness.

[0246] As can be seen from a comparison between Examples 10 and 11, the polar term δ of the Hansen solubility parameter of component (E) P to 4.0MPa 1 / 2 ~10.0MPa 1 / 2 It has been found that by setting the following, even in a composition with a high solid content, the haze value of the cured film of the curable resin composition does not increase, and a cured film of the curable resin composition having excellent surface smoothness and compatibility can be obtained.

[0247] As can be seen from the comparison of Examples 11 to 14, it was found that by setting the content of the (E) component to 0.10 mass % to 0.90 mass % relative to the total mass of the solid contents of the curable resin composition, it is possible to achieve both surface smoothness and compatibility of the cured film of the curable resin composition. [Industrial Applicability]

[0248] According to the present invention, it is possible to suppress contamination of production equipment, etc., caused by volatile matter from a resin film. Therefore, the present invention is expected to further broaden the applications of curable resin compositions and contribute to further development in this field.

Claims

1. (A) an unsaturated group-containing alkali-soluble resin; (E) an acrylic leveling agent; and (F) a solvent; Including, The (A) unsaturated group-containing alkali-soluble resin has an acid value of 25 mgKOH / g to 200 mgKOH / g, The (E) acrylic leveling agent has a weight average molecular weight of 3,000 to 40,000. Curable resin composition.

2. a ratio [Mw(E)] / [Mw(A)] of the weight average molecular weight [Mw(E)] of the (E) acrylic leveling agent to the weight average molecular weight [Mw(A)] of the (A) unsaturated group-containing alkali-soluble resin is 0.5 to 12.0; The curable resin composition according to claim 1.

3. The polar term δ of the Hansen solubility parameter of the (E) acrylic leveling agent Ｐ But 4.0 MPa １／２ ~10.0MPa １／２ That is, The curable resin composition according to claim 1.

4. The content of the (E) acrylic leveling agent is 0.10% by mass to 0.90% by mass based on the total mass of the solid content of the curable resin composition. The curable resin composition according to claim 1.

5. (B) a polymerizable compound having at least two unsaturated groups; (C) an epoxy compound having at least two substituents selected from the group consisting of an oxirane group and an oxetane group; The curable resin composition of claim 1 .

6. A resin film formed from the curable resin composition according to any one of claims 1 to 5.

7. A support; An adherend; An adhesive layer including a resin film of the curable resin composition according to any one of claims 1 to 5, which is disposed between the support and the adherend; A laminate having the following structure:

8. A step of forming an adhesive layer on one or both of a surface of a support and an adherend using the curable resin composition according to any one of claims 1 to 5; a step of adhering the support and the adherend via the formed adhesive layer; A method for producing a laminate comprising the steps of:

9. A semiconductor package comprising the resin film according to claim 6 as an insulating film.

10. A display device comprising the resin film according to claim 6 as an insulating film.

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